Lubricants containing 2, 2-dihaloethylene imines



i be evident.

United States Patent 3,280,032 LUBRICANTS CONTAINING 2,2-DIHALO-ETHYLENE IMINES Joseph M. Sandri, Chicago Heights, and Ellis K. Fields,

Chicago, Ill., assignors to Standard Oil Company, Chicago, Ill., acorporation of Indiana No Drawing. Original application Dec. 15, 1961,Ser.

No. 159,767. Divided and this application Nov. 27, 1963, Ser. No.331,076

2 Claims. (Cl. 252-51) tion contain the structure:

wherein X and Y are each the same or different halides, e.g., F, Cl, Brand I. The preferred halides are Cl and Br.

The chemical compounds containing the above struc- 1 ture will herein bereferred to as 2,2-dihalo ethylenimines which is intended to include2,2-dihalo substituted ethylenimines.

The 2,2-dihalo ethylenimines and 2,2-dihalo substituted ethyleniminesare useful as intermediates in the preparation of pharmaceuticals. Theyare further useful as intermediates in preparing l-chloro acetanilidesfrom imines by addition of a carbon atom between the carbon atom andnitrogen atom at the imine linkage as will hereinafter The l-chloroacetanilides are useful as pesticides and pharmaceutical and dyeintermediates. The oil soluble 2,2-dihalo ethylenimines are particularlyuseful as extreme pressure addition agents of from about 0.05 to about 5weight percent in lubricating oils.

' chlorobromocarbene and dichlorocarbene, as well as mixtures of two ormore imines are also intended. The reaction may advantageously becarried out in the liquid phase at any temperature at which the carbeneand imine exist as such, e.g., at a temperature within the range of fromabout 20 C. to about 140 C. or higher or lower; the temperature of thecarbene-imine reaction is not critical. The reaction usually is completewithin from about 1 to about 48 hours reaction time. It is preferredthat temperature in the range of from about 25 C. to about 50 C. be usedand that the reaction be allowed to proceed to completion in from about4 to about 8 hours reaction time. The dihalo carbene and imine react inequimolar amounts, i.e., one mole of dihalo carbene per mole of -C=Ngroup present in straight chain linkage (non-cyclic). However, it ismore advantageous to use a molar excess of the dihalo carbene based onimine in the reaction because of the instability of the dihalocarbeneand because the dihalo carbene must itself be formed in situduring the reaction since it is a species V Society, 80, 5274 (1958).

to create the dihalo carbene.

3,280,032 Patented Oct. 18, 1966 ICC which does not exist long in thefree state and cannot be isolated as a free chemical compound.

The dihalo carbene is formed in situ in any manner.

For example, at a temperature in the range of about -20 C. to about 140C., the dihalo carbene can be formed by the action of a strong base on ahaloform. Proof of the dihalo carbene is given by W. von E. Doering andW. A. Henderson, in, Journal American Chemical Strong bases have highaffinities for hydrogen halide and set upon the haloform to remove amole of hydrogen halide, leaving the dihalo carbene in situ in thereaction system. The haloform and strong base are used in aboutstoichiometric amounts Thus, in the total reaction in a system of thisinvention, about equimolar amounts of haloform, strong base and imineare mixed together, preferably adding the haloform dropwise orintermittently in aliquots over a period of from about 10 minutes toabout 4 hours, and the total reaction takes place under the conditionsdescribed above to produce the 2,2-dihalo ethylenimines. Advantageouslya molar excess of at least 10% and preferably a molar excess of at least200% of both haloform and strong'base can be used based on imine toassure adequate formation of dihalo carbene. The particular amounts ofthe ingredients added to the system preferably fall within the molarratios of from 1.1 to 6 moles of haloform and 1.1 to 10 moles of strongbase per mole of imine, i.e., per O=N- group in straight chain linkage.The ratio of strong base to haloform is immaterial since any ratiofalling within the above ratios based on imine is sufiicient; howeverthe 4 ratio of both strong base and haloform to imine can be increasedto increase the speed of reaction.

Alternatively, the dihalo carbene can be prepared in situ by thereaction of an alkyl ester, e.g., methyl, ethyl, propyl, ,butyl, etc.ester, of trihalo acetic acid such as ethyl trichloroacetate with astrong base such as sodium methoxide in the presence of the imine.Temperature for this reaction is immaterial within the range where thereactants exist and are preferably in the liquid state. A solvent suchas a hydrocarbon, e.g., hexane, heptane, benzene, toluene, etc. can beused if desired. The trihaloacetic acids include trichloroacetic acid,tribromoacetic acid, bromodichloroacetic acid, iododichloroacetic acid,etc.

As still another method for formation of the dihalo carbene in situ inthe presence of the imine is by thermal decomposition of an alkali oralkaline earth metal salt of trihaloacetic acid in the presence of asolvent at 60 to 150 C. and more usually to C. Carbon dioxide and metalhalide are also formed from the decomposition. Useable solvents are thediethers of glycols or polyglycols, e.g., 1,2-dimethoxy ethane ordiglyme. Examples of the salts of trihaloacetic acids are sodiumtrichloroacetate, potassium tribromoacetate, sodiumbromodichloroacetate, calcium trichloroacetate, barium trichloroacetate,lithium tribromoacetate, etc.

Because the dihalo carbene is known to react with nonaromatic olefinicbonds (see W. von E. Doering et al.

. supra) and because the strong base is known to react with such groups,as, for example, carboxylic acids, sulfonic acids, esters, ketones andthe like, an additional excess of the strong base (where used) and/orhaloform and/or ,as dichlorocarbene, dibromocarbene,'chlorobromocarbene, difluonocarbene, diiodocarbene, etc. Thus, whereany reactions with reactive substituents. 2,2-dihalo ethylenimines canbe prepared from the corresponding imines, because of the possibility ofside reacdihalo is used herein, it is intended that mixed halo such aschloro iodo is included. Accordingly, in the preferred method of forming2,2-dihaloet-hylenirnines, the haloform may be any haloform such aschloroform, brornoform, iodoform, dichlorofluor-omethane,bromodichloromethane, etc.

The strong base where used in preparation of dihalo carbenes may be anystrong base-reacting compound having a metallic or ammonium cation. Allsuch strong 'bases have a sufiiciently high affinity for hydrogen halideto remove them from the haloform. Such strong bases are well known tothose skilled in the art. The preferred 'strong bases are thosecompounds defined by the following structural formula:

a b c wherein M is selected from metal and substituted ammonium cations;Z is selected from oxygen and nitrogen; R is selected from hydrogen, analkyl group containing from 1 to about 19 carbon atoms and an aralkylgroup containing from about 7 to about 19 carbon atoms; a is an integerfrom 1 to 2 inclusive; and b and c are each integers from to 2inclusive.

alkaline earth metal alkoxide-s such as, for example,

sodium methoxide, potassium t-butoxide, calcium ethoxide, ammoniumethoxide, magnesium methoxide, sodium propoxide, lithium ethoxide, andthe like; and other bases such as quaternary ammonium compounds, forexample,

tetraethyl ammonium methoxide, and the like, sodium hydride, lithiumhydride, calcium hydride and the like; sodium amide, calcium amide andthe like; sodium triphenyl methide, potassium triphenylmethide, and thelike; lithium butyl, sodium amyl, potassium phenyl, and

the like.

Any imine, i.e. having the C=N structure, can be subjected to thereaction of this invention to form a new and useful compound inaccordance herewith. The nature of the substituents of the imine isimmaterial to the reaction since, as indicated above, sufiicient amountsof strong base and/ or haloform can be used to complete Although thetion of strong base and/or haloform with reactive substituents, the2,2-dihalo ethylenimine product may not always correspond to thestructure of the imine reactant,

e.g. due to salt formation by strong base with such substituent groupsas SO H, --PO H COOH, or reac tion of hal-oform with substituents orreaction of open chain carbon-to-carbon unsaturation with dihalocarbenes, or destruction of such groups as -NO with strong base; allsuch side reactions are reactions known to the art.

A preferred class of imines which may be reacted in accordance herewithare those imines which correspond to the formula:

sisting of hydrogen, hydrocarbon groups and substituted hydrocarbongroups and R is either a hydrocarbon group or substituted hydrocarbongroup. The substituted hydrocarbon group can have as the substituentsgroups selected from the class consisting of F, -Cl, Br,

NO and N(R) wherein the R represents hydrogen or the same or differenthydrocarbon groups. The

hydrocarbon groups of R R R and R can be hydrocarbon groups includingsaturated and unsaturated aliphatic or aromatic hydrocarbon groups,i.e., alkyl, cycloalkyl, alkenyl and aryl and mixtures thereof such as,for example, alkaryl, alkdienyl, cycloalkyl-aryl, etc. The hydrocarbongroups can have any number of carbon atoms since the hydrocarbon groupdoes not enter into the desired reaction except that substituentsthereon or open chain unsaturation therein may react with strong base,haloform and/or dihalo carbene as indicated herein befiore. Thehydrocarbon group may range in molecular weight, for example, frommethyl up through polycondensed rings and polymeric hydrocarbon groupshaving molecular weights of 100,000 or more, including solid polymerswhich may be dissolved in a suitable nonreactive solvent such asbenzene, toluene, xylene, carbon tetrachloride, or the like. Thepreferred imines are those of the above formula wherein hydrocarbongroups have 1 to 30 carbon atoms (including hydrocarbon groups derivedas polymers of such groups) and those imines wherein the substituentsare selected from --Cl, -Br,

Typical imines which would be useaible in accordance herewith areacetone ethylimine, 2 chlorobutanone methylimine, formaldehyde t-butylimine, hydroxyacetone hexylimine, methyl t-butyl 'ketone dodecylimine,2-hexanone 2,4 dimethylheptadecylimine, isophorone methylimine,benzophenone ethylimine, acetophenone methylirnine, benzalacetophenonephenylimine, benzil ethylimine, acetone phenylimine, Z-butanonenaphthylimine, acetophenone beta-hydroxyethylimine, benzal 2-pyridylimine, benzal benzylimine, benzalacetone n-propylimine,benzylideneaniline, benzal-Z-pyrazineimine, ethylidene benzylimine,benzamidine, benzal naphthenylimine, a-benzaliminonaphthalene 4-sulfonicacid, 3-iminobutane-nitrile, hexydecylimine chloride, benzylidenechloroaniline, benzylidene phenetidine, 2-methylimino butyl mercaptan,3-bromobutanone propylimine, a-benzaliminonaphthalene 4-phosphonic acid,ethylidene methoxypropylimine, ethylidene Z-(distearylamino) ethylimine,benzal a-naphthylimine, 'butylidene u-aminomethyl phosphonic dimethylester, benzal heptadecylaminopropylimine, Z-amylimino butane,N-3,3,S-trimethylcyclohexyl chloral imine, benzal dibutylphenylimine,ethylidene hexylimine, benzal n-octylimine, ibutylidene iso-octylimine,methylidene n-decylimine, benzal cetylimine, ethylidene beta-stearylbeta-methyl imine, octylidene trimeth yloctadecylimine, methylidenehexenylimine, ethylidene N-propargylimine, hydroxyethylidene oleylimine,ethylidene cyclohexylimine, cyclo hexylidene allylcyclohexylimine,benzal diallylcyclohexylimine, tolylidene nonylcyclohexylimine, benzalcyclohexenylimine, ethylidene methylcycloheptadienylimine, ethylidenenaphthylimine, methylidene anthrylimine, N-dodecyl phenylimine,ethylidene xylylimine, aminoethylidene alpha-methyl alpha- I pyridylimine, ethyl-idene pyrrolylimine, furylidene ethylwherein X and Y are asdefined above and R R and R are as defined above with the exception ofvariances in -chain unsaturation.

Other imines having the structure useable in accordance herewith will beevident to those skilled in the art.

Where use of the 2,2-dihalo ethylenimine as an extreme pressure agent isintended, it is advantageous that the R groups (i.e. R R R and R)contain a suflicient number of carbon atoms to provide oil solubility.For such use it is preferred that there be at least a total of 7 carbonatoms in the R groups of the 2,2-dihalo ethylenimine for adequate oilsolubility and that each aryl R group contains from 6 to about 18 carbonatoms and each alkyl (including alkenyl) R group contains from 1 to 20carbon atoms.

As an illustration of this invention, the following examples are given:

Example I A three liter 3-necked round bottom flask, equipped with aheating mantle, stirrer, condenser and dropping funnel, was charged with181.2 g. (1 mole) of N-benzylideneaniline dissolved in '1 liter of drypentane and 378 g. (7 moles) of sodium methoxide. The dropping tunnelwas charged with 4 80 g. (4 moles) of chloroform. About 30 ml. of thechloroform was added to the reaction mixture and the mixture was heatedto reflux to initiate the reaction. The heating mantle was removed andthe remainder of the chloroform was added in portions of 10 to ml. so asto maintain reflux. After all of the chloroform had been added, themixture was stirred for 16 hours and then filtered. The filtrate wasconcentrated in vacuo and the concentrate was cooled in Dry Ice,

whereupon crystallization occurred. The crystals were removed byfiltration and washed with about 200 ml.

of cold pentane. 144 g. (55% yield) of 1,3-diphenyl-2,2-dichloroethylenimine were obtained as a product. The product wasrecrystallized from hexane and had a melting point of 98 99 C.

The product of Example I was subjected to an elemental analysis andmolecular weight determination. The results are listed below incomparison with the theoretical analyses for1,3-diphenyl-2,2-dichloroethylenirmne.

Analysis Example Theoretical Wt. Percent C 6 6 2 2 Molecular Weight 2626 The structure of 1,3-diphenyl-2,2-diohloroethylenimine was furthersubstantiated by infra-red analysis and nuclear magnetic resonanceanalysis. The infra-red spectrum contains a peak corresponding to theC01 grouping and the nuclear magnetic resonance spectrum is consistentwith the proposed structure for the compound.

To further substantiate the structure of the 2,2-dihalo ethyleniminesprepared in the example, the prepared compound was hydrolyzed to form aknown compound, properties of which were compared with the knownproperties phenyl-Z,2-dichloroethylenimine was obtained.

Elemental analysis appeared as follows:

. Calculated for Found in Elements C HmONCl Compound of Example o 68.468.35 H 4.89 4.92 0 6.52 6.45 N 5.7 5.23 01 14.5 14.1

Example [I This example illustrates the preparation ofl-p-chlorophenyl-3-phenyl-2,2-dichloroethylenimine. To a stirred slurryof 21.6 g. (0.1 mole) of benzylidene p-chloroaniline, M.P. 60-61(reported: M.P. 62), 44.9 g. (0.4 mole) of potassium t-butoxide and 250ml. of hexane was slowly added 47.8 g. (0.4 mole of chloroform. Thereaction mixture was stirred at room temperature for 16 hours. Themixture was filtered with the aid of suction, the residue was washedthree times with hexane and the solvent was removed in vacuo from thecombined filtrates leaving a solid, crystalline product. After onerecrystallization from pentane 20.4 g. (68%) of 1-p-chlorophenyl-3- Uponfurther recrystallization from pentane the product was obtained aslight-tan crystals, M.P. 71-72". The band at 6.2 microns which waspresent in the infra-red spectrum of the starting material was absent inthe product. Analysis was as follows:

Calculated for C H Cl N: C, 56.31; H, 3.38; Cl, 35.62; N, 4.69. Found:C, 55.68; H, 3.69; Cl, 35.2; N, 4.44.

To further substantiate the structure of the product of Example II, andto illustrate its use as an intermediate for preparation ofalpha-chloro-alpha-phenyl-p-chloroacetanilide, a portion of thel-p-chlorophenyl-3-phenyl- 2,2-dichloroethylenimine was allowed to standin an excess of water at room temperature for 24 hours. The

starting material was hydrolyzed to producealpha-chloroalpha-phenyl-p-chloroacetanilide in a quantitative yield.The product crystallized from ethanol as colorless .needles, M.P. -461C. Analysis was as follows:

Calculated for C H Cl NO: C, 60.02; H, 3.96; Cl, 25.31; N, 5.00. Found:C, 59.80; H, 4.22; Cl, 24.8; N, 4.66.

Example III This example illustrates the preparation ofl-p-ethoxyphenyl-3-phenyl-2,2-dichloroethyleninmine. A total of 47.8 g.(0.4 'mole) of chloroform was slowly added to a stirred mixture of 22.5g. (0.1 mole) of benzylidene pphenetidine (light-yellow plates from 95ethanol, M.P. 7274, reported M.P. 76, 44.9 g. (0.4 mole) of potassiumt-butoxide and 350 ml. of hexane. The reaction mixture was stirred atroom temperature for 18 hours. The mixture was heated to reflux andfiltered with the aid of suction, the residue was washed with hot hexaneand the solvent was removed from the combined filtrates in vacuo leaving28.2 g. (91%) of a crude, crystalline residue. The product,1-p-ethoxy-phenyl-3-phenyl-2,2-dichlo-roethylenimine, crystallized fromhexane in the form of colorless plates, M.P. 76.5-77.5 C. The band at6.2 microns which was present in the infra-red spectrum of the startingmaterial was absent in the product. Analysis was as follows:

Calculated for C H C1 NO: C, 62.35; H, 4.91; Cl, 23.01; N, 4.55. Found:C, 63.50; H, 5.37; Cl, 19.0; N, 4.34.

(The analysis was run the same day as submittal. However, a strongevolution of hydrogen chloride gas was noted upon return of the samplethat same day.)

1 Synthesized by a procedure patterned after that found in olz gfilpii:Synthesis, vol. I, p. 80.

'To further substantiate the .identity of the product of Example III andas an illustration of its use as an intermediate,alpha-chloro-alpha-phenyl-p-ethoxyacetanilide was formed from theproduct as follows: A mixture of an1-p-ethoxyphenyl-3-phenyl-2,2-dichloroethylenimine and excess water wasboiled for five minutes. After a strong evolution of hydrogen chloridegas a solid product, alpha- -chloro-alpha-phenyl-p-ethoxyacetanilide,was produced in a quantitative yield. The product crystallized frommethanol as colorless plates, M.P. 145-1465 C. Analysis was as follows:

Calculated: C, 66.32%; H, 5.57%; N, 4.83%. .43%; H, 5.91%; N, 4.76%.

The 2,2-dihalo ethylenimines of this invention are particularly usefulas extreme pressure addition agents for addition to lubricating oils. Asan example of the extreme pressure imparting properties of suchcompounds, 2% of the compound of Example I was added to asolventextracted 30 base mineral oil and was subjected to extremepressure tests on an Almen machine. The base oil alone was also tested;2 runs were made for each sample. The results of the Almen machine testswere as follows:

Sample Pass,

Fail, lb. 1b.

8 10 Base 011 alone 8 10 The above data show that the1,3-diphenyl-2,2-dichloro ethylenimine markedly increases the loadcarrying ability of the base oil.

The compositions described herein can be used as indicated above invarying amounts of from about 0.05 to about 5 weight percent as extremepressure agents in lubricating oils. Although the present invention hasbeen illustrated by the use of the additive compositions in minerallubricating oils, it is not restricted thereto. Other lubricating oilbases can be used, such as hydrocarbon oils, both natural and synthetic,for example, those obtained by the polymerization of olefins, as Well assnythetic lubricating oils of the alkylene oxide type and the mono andpolycarboxylic acid ester type, such as the oil soluble esters ofpelargonic acid, adipic acid, sebacic acid, azelaic acid, etc. It isalso contemplated that various other well known additives, such asanti-oxidants, anti-foaming agents, pour point depressors, extremepressure agents, anti-wear agents, may be incorporated in lubricatingoils containing the additives of our invention.

Concentrates of a suitable oil base containing more than 2%, for exampleup to 30% or more,of the additives of this invention alone or incombination with other additives can be used for blending withhydrocarbonoils or other oils in the proportions desired for theparticular conditions of use to give a finished lubricating productcontaining the additives of this invention.

Unless otherwise stated, the percentages given herein and in the claimsare percentages by weight.

It is evident that we have provided certain new and useful compositionsof matter and have also provided a method for making such compositions.The compositions are the 2,2-dihalo ethylenimine's containing thestructure:

wherein X and Y are each halide and R and R are selected from the classconsisting of alkyl, aryl and hydrogen, R is selected from the classconsisting of alkyl and aryl and R R and R contain at least about 7total carbon atoms to provide oil solubility.

2. A lubricant composition which comprises a major amount of lubricatingoil and a minor amount suflicient 'to impart extreme pressure propertiesto said composition of a 2,2-dihaloethyleue imine selected from thegroup consisting of 1,3-diphenyl-2,2-dichloroethyleneimine,1-pchlorophenyl-3-phenyl-2,2-dichloroethyleneimine and1-pethoxyphenyl-3-phenyl-2,2-dichloroethyleneimine.

References Cited by the Examiner UNITED STATES PATENTS 6/1938 Prutton2525l X 6/1959 Filbey et a1. 252-51 X DANIEL E. WYMAN, Primary Examiner.

P. P. GARVIN, Assistant Examiner.

1. AN EXTREME PRESSURE LUBRICANT COMPOSITION WHICH COMPRISES ALUBRICATING OIL CONTAINING A SMALL AMOUNT SUFFICIENT TO IMPART EXTREMEPRESSURE PROPERTIES OF AN OILSOLUBLE CHEMICAL COMPOUND HAVING THEFOLLOWING STRUCTURAL FORMULA: